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CAS No. : | 171178-46-4 | MDL No. : | MFCD09258838 |
Formula : | C11H13ClN2O4 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | KOSPRFUMGCNGFJ-UHFFFAOYSA-N |
M.W : | 272.69 | Pubchem ID : | 10564144 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H332-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With trifluoroacetic acid In dichloromethane | 5-Amino-2-chloropyridine-4-carboxylic acid. A stirred suspension of 5-[N-(tert-butoxycarbonyl)amino]-2-chloropyridine-4-carboxylic acid (1.91 g, 7 mmol) in CH2 Cl2 (200 mL) is treated slowly with trifluoroacetic acid until homogeneous (ca. 12 mL). The solution is stirred overnight and extracted with dilute NH4 OH, and the aqueous layer is then acidified with dilute HCl to gave a precipitate of 5-amino-2-chloropyridine-4-carboxylic acid (1.05 g, 87percent yield). 1 H NMR (DMSO) δ 9.01 (2H, m), 8.03 (1H, s), 7.48 (1H, s). |
80% | With trifluoroacetic acid In dichloromethane at 20℃; | Step (d): 5-AMINO-2-CHLORO-ISONICOTINIC acid A suspension of 5-tert-butoxycarbonylamino-2-chloro-isonicotinic acid in methylene chloride (600mL) was treated dropwise at room temperature with TFA until the solid had dissolved into solution (95 mL). The reaction mixture was stirred overnight under nitrogen at room temperature, evaporated to dryness, diluted with water, and the solid collected by filtration. The solid was washed with water, dried under low heat and house vacuum, to afford 19.55g of 5-amino- 2-chloro-isonicotinic acid as a yellow solid (93.6percent yield). 1H NMR (400 MHz, DMSO-D6) 8 ppm 7.5 (s, 2H), 8.0 (s, 2H) MS (APCI) M+1= 173.0; Step (d): 5-AMINO-2-CHLORO-ISONICOTINIC acid A 3 L round bottomed flask was charged with 5-tert- BUTOXYCARBONYLAMINO-2-CHLORO-ISONICOTINIC acid (138 g, 0.51 moles), 1 L of CH2C12, and 400 mL of TFA. The resulting orange solution was stirred overnight at room temperature. One liter of H20 was added to the reaction solution, which caused a solid to precipitate out. The solid was collected, washed once with H2O and dried overnight in the vacuum oven at 45°C. The reaction yielded 69.6 g (80percent total yield) of 5-amino-2-chloro-isonicotinic acid as a pale yellow solid, which was pure enough by NMR to use in the next reaction. ON (DMSO) 7.99 (1 H, d), 7.45 (1 H, d) MS [M+H] + 173 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69.3% | Stage #1: With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In hexanes; diethyl ether at -75 - -10℃; for 2 h; Stage #2: at -75 - 20℃; Stage #3: With hydrogenchloride In water |
Step (c): 5-TERT-BUTOXYCARBONYLAMINO-2-CHLORO-ISONICOTINIC acid A suspension of (6-CHLORO-PYRIDIN-3-YL)-CARBAMIC acid tert-butyl ester in 800mL of ether was treated with TMEDA, and the mixture cooled TO-75°C. To this was added 1.6M BuLi in hexanes dropwise while keeping the temperature BELOW-65°C. After the addition was complete, the reaction mixture was allowed to warm to-15°C TO-10°C, and stirred in this temperature range for 2 hours. The reaction mixture was again cooled TO-75°C, and dry carbon dioxide was bubbled into the mixture for 3 hours before allowing the reaction to warm to room temperature overnight with continued bubbling of carbon dioxide. The reaction mixture was carefully quenched with 20percent aqueous ammonium hydroxide solution (1.8L), the aqueous portion extracted with ether, then acidified to pH 5 using 50percent aqueous HCI. The resulting solid was collected by filtration, washed with water, and dried to give 33.07g (69. 3percent yield) of 5-tert- butoxycarbonylamino-2-chloro-isonicotinic acid as a light yellow solid. 1H NMR (400 MHz, DMSO-D6) d ppm 1.5 (s, 9H), 7.7 (s, 1H), 9.1 (s, 1H), 10.0 (s, 1H) MS (APCI) M+1 = 273.1 |
60% | Stage #1: With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In tetrahydrofuran; hexanes at -75 - -15℃; for 1 h; Stage #2: at -35 - 20℃; Stage #3: With hydrogenchloride In water |
Step (c): 5-TERT-BUTOXYCARBONYLAMINO-2-CHLORO-ISONICOTINIC acid The reaction was run under Argon. A 20 L jacketed reactor was charged with (6-chloro-pyridin-3-yl)-carbamic acid tert-butyl ester (200 g, 0. 875 moles), THF (5 L), and TMEDA (304 ML, 2.3 equivalents, 2 wtpercent water), and the mixture was cooled to BETWEEN-70°C AND-75°C. nBuLi (805 ML, 2.5 M in hexanes, 2.3 mole equivalents) was added via dropping funnel at a rate that kept the reaction temperature BETWEEN-70°C AND-75°C. The resulting brown solution was warmed to-15°C and stirred for 1 hour. The reaction mixture was then cooled back to- 35°C, and a lecture bottle of C02 was bubbled through. The reaction mixture was allowed to warm to 20°C over 2 hours, during which time the solution became an orange slurry. The reaction mixture was stirred at room temperature overnight. The reaction was quenched by the addition of 1.5 L of water. During the quench a precipitate formed in the aqueous layer. The layers were separated, taking the precipitated solid with the aqueous layer. The organic layer was washed once with 1 N NaOH. The aqueous portions were combined, and the pH adjusted to pH 2 with 6 N HC1. The solid was collected by filtration, washed twice with water and dried overnight in the vacuum oven at 45°C. The reaction yielded 143 g (60percent total yield) of 5-tert-Butoxycarbonylamino-2-chloro-isonicotinic acid as a tan solid that was sufficiently pure by NMR to use in the next reaction. ON (DMSO) 10.06 (1 H, s), 9.07 (1 H, s), 7.71 (1 H, d), 1.42 (9 H, s) MS [M+H] + 273 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In diethyl ether | 5-[N-(tert -Butoxycarbonyl)amino]-2-chloropyridine-4-carboxylic acid. A solution of 5-[N-(tert-butoxycarbonyl)amino]-2-chloropyridine (22.87 g, 0.1 mol) and TMEDA (47 mL, 0.31 mol) in dry Et2 O (600 mL) is cooled to -78° C., and n-BuLi (10M in hexanes, 30 mL, 0.3 mol) is added dropwise. The solution is allowed to warm to -10° C. and is then kept at that temperature for 2 h, before being recooled to -78° C. Dry CO2 is then bubbled in, and the resulting mixture is allowed to warm to 20° C., before being quenched with water (300 mL) containing a small amount of NH4 OH. The resulting aqueous layer is washed with EtOAc, then acidified slowly with dilute HCl to precipitate 5-[N-(tert-butoxycarbonyl)amino]-2-chloropyridine-4-carboxylic acid (15.5 g, 57percent). 1 H NMR (DMSO) δ 10.00 (1H, s), 9.13 (1H, s), 7.74 (1H, s), 1.47 (9H, s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | at -78 - 0℃; for 2 h; | A stirred solution of (6-chloro-pyridin-3-yl)-carbamic acid tert-butyl ester (3.28 g, 14.3 mmol) and TMEDA (6.7 mL, 44.4 mmol) in Et2O (100 mL) at -78° C. was treated with n-BuLi (4.3 mL, 10 M, 43 mmol). After stirring the mixture at -78° C. for 2 hours CO2 was bubbled into the reaction and the solution was warmed to 0° C. Water was added and the mixture was extracted with EtOAc. The aqueous layer was acidified and extracted with Et2O. The Et2O layer was washed with brine, dried (MgSO4) and the solvent was removed in vacuo. The residual solid was triturated with Hexane/Et2O to give 25A (1.38 g, 35percent) HPLC Rt=2.98 min. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.1 g | Reflux; Inert atmosphere | [00480] To a stirred solution of 5-tert-butoxycarbonylamino-2-chloro-isonicotinic acid (crude, 8.0 g) in methanol (50 mL) was added H2SO4 (5.0 mL). The mixture was then heated to reflux overnight. The reaction was cooled to room temperature and was concentrated in vacuum. The residue was diluted with water. The aqueous mixture was neutralized with sat. NaHCC>3 to pH = 8 and extracted with EA (100 mL x2). The combined organic layers were washed with brine (50 mL), dried over anhydrous Na2S04 and filtered. The filtrate was evaporated in vacuum to residue, which was purified by silica gel |
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